JPH0588697B2 - - Google Patents
Info
- Publication number
- JPH0588697B2 JPH0588697B2 JP61134672A JP13467286A JPH0588697B2 JP H0588697 B2 JPH0588697 B2 JP H0588697B2 JP 61134672 A JP61134672 A JP 61134672A JP 13467286 A JP13467286 A JP 13467286A JP H0588697 B2 JPH0588697 B2 JP H0588697B2
- Authority
- JP
- Japan
- Prior art keywords
- phthalic acid
- reaction
- range
- chloride
- yield
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 25
- -1 alkali metal salt Chemical class 0.000 claims description 22
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 5
- 150000001447 alkali salts Chemical class 0.000 description 5
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 5
- 229940045803 cuprous chloride Drugs 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- HQWKKEIVHQXCPI-UHFFFAOYSA-L disodium;phthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C([O-])=O HQWKKEIVHQXCPI-UHFFFAOYSA-L 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000954 titration curve Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はフタル酸ジメタリルエステルの製造法
に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing phthalic acid dimethallyl ester.
フタル酸ジメタリルエステルはその重合物が透
明性、高屈折率、表面硬度等の光学特性に優れ、
特に光学用材料として期待されているものであ
る。 The polymer of phthalic acid dimethallyl ester has excellent optical properties such as transparency, high refractive index, and surface hardness.
It is particularly expected to be used as an optical material.
フタル酸のアルカリ金属塩とハロゲン化アリル
とを塩化第一銅の存在下で反応させて、フタル酸
ジアリルエステルを製造する方法として、反応時
の溶液のPHを規定する特許が今迄に提案されてい
る。
Until now, patents have been proposed that specify the pH of the solution during the reaction as a method for producing phthalic acid diallyl ester by reacting an alkali metal salt of phthalic acid with an allyl halide in the presence of cuprous chloride. ing.
すなわち、特公昭39−19785においては、反応
時の溶液のPHを約４〜８の範囲に規定すること、
又、特開昭54−130528においてはPHを６〜８に調
整することが記載されている。 That is, in Japanese Patent Publication No. 39-19785, the pH of the solution during the reaction must be specified in the range of about 4 to 8;
Further, in Japanese Patent Application Laid-Open No. 54-130528, it is described that the pH is adjusted to 6 to 8.
この様にフタル酸ジアリルエステルの製造にお
いては、反応時のPHを弱酸性下に調整している
が、これらの方法をフタル酸ジメタリルエステル
の製造に適用しても意外な事に好ましい結果が得
られない。 In this way, in the production of phthalic acid diallyl ester, the pH during the reaction is adjusted to a weakly acidic state, but surprisingly, favorable results were obtained even when these methods were applied to the production of phthalic acid dimethallyl ester. I can't get it.
フタル酸のアルカリ塩とメタリルクロライドと
を塩化第一銅の存在下で反応させる際、従来の方
法では目的物の収率が満足すべき段階になく、更
に改良が望まれていた。本発明は高収率で目的物
を得る改良法を提供しようとするものである。
When an alkali salt of phthalic acid and methallyl chloride are reacted in the presence of cuprous chloride, the yield of the target product is not at a satisfactory level with conventional methods, and further improvements have been desired. The present invention seeks to provide an improved method for obtaining the desired product in high yield.
フタル酸のアルカリ塩とメタリルクロライドと
の脱食塩反応によるフタル酸ジメタリルエステル
を製造する際、出発原料のフタル酸のアルカリ塩
については入手の容易さ、経済面から無水フタル
酸を使用するのが一般的である。無水フタル酸の
中和によつて得られるフタル酸アルカリ金属塩を
用いてメタリルクロライドと反応させると目的物
であるフタル酸ジメタリルエステルの収率が意外
に低い。この原因追求のため無水フタル酸の中和
滴定曲線を詳細に検討すると第１図に示す如く、
意外にも中和点はPH８をやや越えた所にあること
が判つた。これよりPHがちようど８でもフタル酸
のアルカリ塩の形成が不充分であり、これより低
い時は更に不充分となる。
When producing phthalic acid dimethallyl ester through a desalting reaction between an alkali salt of phthalic acid and metallyl chloride, it is preferable to use phthalic anhydride as the starting material for the alkali salt of phthalic acid due to its ease of availability and economical aspects. is common. When an alkali metal phthalate salt obtained by neutralizing phthalic anhydride is used to react with methallyl chloride, the yield of the target product, dimethallyl phthalate, is surprisingly low. In order to investigate the cause of this, a detailed study of the neutralization titration curve of phthalic anhydride revealed that as shown in Figure 1,
Surprisingly, the neutralization point was found to be slightly above PH8. Even if the pH is higher than this, 8, the formation of alkali salts of phthalic acid is insufficient, and when the pH is lower than this, it is even more insufficient.
本発明のフタル酸のアルカリ塩とメタリルクロ
ライドの反応が完結しない理由の１つに従来行わ
れている４〜８の範囲のPH調整が考えられる。
又、もう一つの出発原料であるメタリルクロライ
ドの水溶液中の安定性について詳細検討するとア
リルクロライドと異り溶液が酸性になると急激に
低下することが判つた。更にメタリルクロライド
が加水分解して生成したメタリルアルコールは酸
性側でイソブチルアルデヒドへ容易に異性化して
しまうので、加水分解は時間に比例してどんどん
進行してしまう。 One of the reasons why the reaction between the alkali salt of phthalic acid and methallyl chloride of the present invention is not completed is considered to be the conventional pH adjustment in the range of 4 to 8.
Further, when we investigated in detail the stability of methallyl chloride, another starting material, in an aqueous solution, we found that, unlike allyl chloride, its stability decreases rapidly when the solution becomes acidic. Furthermore, since methallyl alcohol produced by hydrolysis of methallyl chloride is easily isomerized to isobutyraldehyde on the acidic side, hydrolysis progresses rapidly in proportion to time.
以上の詳細検討結果を踏まえて、本発明者らは
収率の向上を計るべく鋭意検討を行い、本発明を
完成するに至つた。 Based on the results of the above detailed study, the present inventors conducted intensive studies to improve the yield, and finally completed the present invention.
すなわち本発明は、フタル酸のアルカリ金属塩
とメタリルクロライドとを塩化第一銅の存在下反
応させてフタル酸ジメタリルエステルを製造する
際、該反応のPHを８を越えて12.5の範囲で反応せ
しめることを特徴とする製造法である。反応液の
PHを上記の８を越えて13の範囲に保つことによ
り、従来法では達成出来なかつた高収率で該目的
物を得ることが可能となつた。 That is, the present invention provides that when producing phthalic acid dimethallyl ester by reacting an alkali metal salt of phthalic acid and methallyl chloride in the presence of cuprous chloride, the pH of the reaction is in the range of over 8 and 12.5. This is a manufacturing method characterized by reaction. of reaction solution
By keeping the pH in the range of 13, exceeding the above 8, it became possible to obtain the desired product in a high yield that could not be achieved by conventional methods.
以下に本発明を詳細に説明する。 The present invention will be explained in detail below.
フタル酸のアルカリ金属塩は通常はソーダ塩で
ある。フタル酸のアルカリ金属塩は通常は無水フ
タル酸を所定量のアルカリ水溶液に加え、必要で
あれば加熱してフタル酸のアルカリ金属塩とす
る。この際の水量は通常はフタル酸１モルあた
り、140〜500mlの範囲で使用するが、この範囲外
でも良い。メタリルクロライドとフタル酸のアル
カリ金属塩との反応仕込モル比はフタル酸のアル
カリ金属塩１モルあたり化学量論的に必要な２以
上が必要であり、この値が大きくなる程フタル酸
のアルカリ金属塩基準の収率は向上する。しか
し、メタリルクロライドの損失が大となるので、
経済的には出来るだけ過剰率を下げるのが望まし
く、通常は２〜３の範囲内で行う。 The alkali metal salt of phthalic acid is usually the soda salt. The alkali metal salt of phthalic acid is usually prepared by adding phthalic anhydride to a predetermined amount of aqueous alkaline solution and heating if necessary. The amount of water used at this time is usually in the range of 140 to 500 ml per mole of phthalic acid, but it may be outside this range. The reaction charge molar ratio of methallyl chloride and alkali metal salt of phthalic acid must be at least 2, which is stoichiometrically required per mole of alkali metal salt of phthalic acid. The yield based on the metal salt is improved. However, since the loss of methallyl chloride is large,
Economically, it is desirable to lower the excess rate as much as possible, and it is usually carried out within the range of 2 to 3.
本発明の反応には第一銅特に塩化第一銅を触媒
として使用する。この触媒の通常の使用量はフタ
ル酸のアルカリ金属塩１モルあたり、0.005〜0.1
モルの範囲である。 Cuprous, especially cuprous chloride, is used as a catalyst in the reaction of the invention. The usual amount of this catalyst used is 0.005 to 0.1 per mole of alkali metal salt of phthalic acid.
It is in the molar range.
本発明の方法は反応中のPH調節を８を越えて13
の範囲に保つこと、好ましくはPH９〜12.5の範囲
に保つことが重要である。これよりPHが低下する
と目的物の収率が低下する。又、この範囲よりPH
を高くすることは経済的に得策ではない。 The method of the present invention allows pH control during the reaction to exceed 8.13
It is important to keep the pH within the range of 9 to 12.5, preferably within the range of 9 to 12.5. When the pH is lower than this, the yield of the target product decreases. Also, from this range PH
It is not economically advisable to raise the
PHの調節はNaOH，NaHCO3，Na2CO3等を反
応開始時または反応中に反応系に添加することに
より達成される。 Adjustment of PH is achieved by adding NaOH, NaHCO 3 , Na 2 CO 3 or the like to the reaction system at the start of the reaction or during the reaction.
反応温度は35℃から反応液の沸騰温度まで採る
ことが可能であり、反応温度によつて反応時間も
数時間から10時間程度の範囲を採用できる。 The reaction temperature can range from 35°C to the boiling temperature of the reaction solution, and the reaction time can range from several hours to about 10 hours depending on the reaction temperature.
反応後、必要に応じて抽剤を加え、有機層を水
相から分離し、水洗後、溶剤、低沸点成分を蒸留
分離し、ついで目的物であるフタル酸ジメタリル
エステルを蒸留取得する。 After the reaction, an extractant is added as necessary to separate the organic layer from the aqueous phase, and after washing with water, the solvent and low-boiling components are separated by distillation, and then the target product, phthalic acid dimethallyl ester, is obtained by distillation.
以下に本発明を実施例によつて具体的に示す。
尚、実施例中の部は重量部を表わす。 The present invention will be specifically illustrated below using Examples.
In addition, parts in the examples represent parts by weight.
実施例 １
撹拌機、還流冷却器、PHメーターおよび温度計
を付した反応器に40％フタル酸ソーダ水溶液525
部、重ソウ50.5部、塩化第一銅２部を入れ、PHを
9.5に調整する。ついでメタリルクロライド226部
を加え、撹拌下、反応液を40℃で４時間、ついで
１時間還流下に加熱した。又、この間のPHは9.0
〜9.5に保つた。反応終了後、ヘキサン150部、水
100部を加えて有機層を分離し、水洗後、蒸留操
作により溶剤および低沸留分を留去したのち、目
的物のフタル酸ジメタリルエステルを261部得た。
フタル酸ソーダ基準の収率95.2％である。Example 1 40% sodium phthalate aqueous solution 525 was placed in a reactor equipped with a stirrer, reflux condenser, PH meter and thermometer.
1 part, 50.5 parts of heavy sodium chloride, and 2 parts of cuprous chloride, and adjust the pH.
Adjust to 9.5. Then, 226 parts of methallyl chloride were added, and the reaction mixture was heated at 40° C. for 4 hours and then under reflux for 1 hour while stirring. Also, the pH during this time was 9.0
I kept it at ~9.5. After the reaction is complete, add 150 parts of hexane and water.
After adding 100 parts of the organic layer and separating the organic layer, washing with water and distilling off the solvent and low-boiling fraction, 261 parts of the target product, phthalic acid dimethallyl ester, were obtained.
The yield is 95.2% based on sodium phthalate.
実施例 ２
反応液のPHを12.0〜12.5に調整する以外は実施
例１と同様の操作を行い、フタル酸ジメタリルエ
ステルをフタル酸ソーダ基準で95.5％の収率で得
た。Example 2 The same operation as in Example 1 was performed except that the pH of the reaction solution was adjusted to 12.0 to 12.5, and phthalic acid dimethallyl ester was obtained in a yield of 95.5% based on sodium phthalate.
比較例
実施例１において、重ソウの添加を止め、替り
にカセイソーダ水溶液を反応液のPHが７〜7.5に
なるように添加して反応を行つた。Comparative Example In Example 1, the reaction was carried out by stopping the addition of sodium chloride and instead adding an aqueous solution of caustic soda so that the pH of the reaction solution was 7 to 7.5.
その結果、フタル酸ジメタリルエステルをフタ
ル酸ソーダ基準で79.9％の収率を得た。 As a result, a yield of 79.9% of phthalic acid dimethallyl ester was obtained based on sodium phthalate.
第１図は無水フタル酸1.0098ｇをＮ／10NaOH
溶液で滴定した際の中和曲線図を示す。
Figure 1 shows 1.0098g of phthalic anhydride in N/10NaOH
A neutralization curve diagram when titrating with a solution is shown.
Claims (1)
イドとを第一銅の存在下で反応させるにあたり、
反応液のPHを８を越えて13の範囲で反応せしめる
ことを特徴とするフタル酸ジメタリルエステルの
製造方法。 ２ 反応液のPHが９〜12.5の範囲であることを特
徴とする特許請求の範囲第１項記載の方法。[Claims] 1. In reacting an alkali metal salt of phthalic acid and methallyl chloride in the presence of cuprous,
A method for producing phthalic acid dimethallyl ester, characterized in that the reaction is carried out at a pH of a reaction solution exceeding 8 and in the range of 13. 2. The method according to claim 1, wherein the pH of the reaction solution is in the range of 9 to 12.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61134672A JPS62292746A (en) | 1986-06-10 | 1986-06-10 | Production of dimethallyl phthalate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61134672A JPS62292746A (en) | 1986-06-10 | 1986-06-10 | Production of dimethallyl phthalate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62292746A JPS62292746A (en) | 1987-12-19 |
| JPH0588697B2 true JPH0588697B2 (en) | 1993-12-24 |
Family
ID=15133867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61134672A Granted JPS62292746A (en) | 1986-06-10 | 1986-06-10 | Production of dimethallyl phthalate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62292746A (en) |
-
1986
- 1986-06-10 JP JP61134672A patent/JPS62292746A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62292746A (en) | 1987-12-19 |
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